CN100435387C - Battery separator - Google Patents

Battery separator Download PDF

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Publication number
CN100435387C
CN100435387C CNB2004800344615A CN200480034461A CN100435387C CN 100435387 C CN100435387 C CN 100435387C CN B2004800344615 A CNB2004800344615 A CN B2004800344615A CN 200480034461 A CN200480034461 A CN 200480034461A CN 100435387 C CN100435387 C CN 100435387C
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China
Prior art keywords
battery
layer
negative electrode
barrier film
ion
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CN1883064A (en
Inventor
S·M·戴维斯
J·M·鲍尔顿
C·埃尔姆
O·毛
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Gillette Co LLC
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Gillette Co LLC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A battery includes a separator with a trapping layer that traps dissolved metal ions.

Description

Battery diaphragm
The present invention relates to battery.
Battery, for example alkaline battery is used as power supply usually.In general, battery contains negative pole (anode) and anodal (negative electrode).Anode contain can be oxidized active material (for example, zinc granule); Contain the active material (for example, manganese dioxide) that can be reduced with negative electrode.The active material of anode can reduce the active material of negative electrode.For the active material that prevents anode and the active material of negative electrode directly react, electrode is each other by barrier film (separator) electric insulation.
When battery during as the power supply of device such as mobile phone, electrode is electrically contacted, thereby make electronics can flow through this device and allow to take place respectively oxidation and reduction reaction so that electric power to be provided.The electrolyte that contacts with electrode contains the ion of the barrier film between the electrode of flowing through, to keep the charge balance of entire cell in discharge process.
On the one hand, the invention is characterized in have electrolyte, the negative electrode of (for example, cupric oxide) that contains active material and the alkaline battery of laminated diaphragm.Laminated diaphragm comprise have the component of catching (for example, metal) catch layer.In some cases, active material of cathode may be dissolved in the electrolyte, thereby forms the metal ion (for example, metal cation, multi-atomic ion) of the dissolving that may reduce battery capacity and/or storage life.Catch that layer can reduce and/or the metal cation component of the metal ion of these dissolvings of sorption, thereby improve the storage life and/or the capacity of battery.
On the one hand, the invention is characterized in battery.The barrier film of this battery has the layer of the material of the metal cation component that contains the ion that can reduce dissolving.
On the other hand, the invention is characterized in battery.This battery has the negative electrode that contains cupric oxide, the anode that contains zinc and the barrier film between negative electrode and anode.This barrier film has the ground floor that contains glassine paper, and the second layer of bismuth-containing contains the 3rd layer of zirconium dioxide and contains the 4th layer of non-woven material.
With reference to the accompanying drawings, specification and claim, other aspects, features and advantages of the present invention will become apparent.
Fig. 1 is the cross sectional view of the embodiment of battery.
Fig. 2 is the schematic diagram of the embodiment of barrier film.
Fig. 3 is the schematic diagram of another embodiment of barrier film.
Fig. 4 is the schematic diagram of the 3rd embodiment of barrier film.
Fig. 5 is the schematic diagram of the 4th embodiment of barrier film.
With reference to figure 1, battery or electrochemical cell 10 comprise the cylinder blanket 18 that contains negative electrode 12, anode 14 and the barrier film between negative electrode and anode 16.Negative electrode 12 comprises active copper material (for example, cupric oxide), and anode 14 comprises active zinc material.Battery 10 also comprises current-collector 20, seal 22 and casting coping 24 (it serves as the negative terminal of battery).Negative electrode 12 contacts with shell 18, and the anode of battery 10 is positioned at battery 10 end relative with negative terminal.Electrolyte is dispersed in the entire cell 10.
In some cases, electrolyte solubilized active material of cathode (for example, copper product).For example, if electrolyte is a dense relatively alkaline electrolyte (for example potassium hydroxide) and if negative electrode contains the copper product such as CuO, then electrolyte solubilized copper product forms Cu (OH) 4 2-Ion.Cu (OH) 4 2-Ion can be diffused into anode 14 then, and they form the copper metal and consume zinc at this:
(1)Zn+Cu(OH) 4 2-→Zn(OH) 4 2-+Cu
When the two was consumed when active material of cathode and active material of positive electrode, the capacity of battery descended.In some cases, the copper metal causes at anode 14 place's liberations of hydrogen, thus the pressure in the increase battery, and cause battery exhaust and leakage potentially.In addition, the copper metal can form the dendrimer (dendrite) of extending to negative electrode from anode.This dendrimer penetrable septum also contacts with negative electrode, thereby makes battery short circuit.Therefore, can shorten and/or be unreliable the storage life of battery.Structure barrier film 16 is with restriction or prevent active material of positive electrode and from the contact between the metal ion of the moving dissolving of active material of cathode.Owing to have barrier film 16, so battery 10 can experience the probability decline of short circuit and/or aerogenesis.As a result, battery 10 so may exhaust and its inner content of leakage.Owing to these reasons and other reason, barrier film 16 can improve the storage life and the capacity of battery 10.In addition, barrier film 16 can be realized these advantages, simultaneously nontoxic relatively and/or environmental friendliness.
Barrier film 16 comprises one or more layers selective membrane, catches layer and/or non-woven layer.
With reference to figure 2, barrier film 16 has multilayer (that is, greater than one deck) structure, and described sandwich construction has to be bonded on the selective membrane 52 and to be bonded at opposite side in a side catches layer 50 on the non-woven layer 54.In Fig. 2, selective membrane 52 is positioned at negative electrode 12 next doors, and non-woven layer 54 is positioned at anode 14 next doors.
When the metal ion from the dissolving of active material of cathode passes when catching layer 50, catch that layer reduces and/or the metal cation component of the metal ion of sorption (for example, absorption and/or absorb) dissolving.For example, catch the layer can with Cu (OH) 4 2-Ion (metal ion of dissolving) reaction is to go back native copper (II) (Cu (OH) 4 2-The metal cation component of ion), thus form the copper metal.Catch the gel-in-matrix that layer 50 comprises solvent and ion-permeable, for example poly-(acrylic acid), poly-(vinyl alcohol), poly-(oxirane), poly-(vinylpyrrolidone), poly-(acrylamide), poly-(vinyl butyral) or poly-(4-styrene sulfonic acid).Catch layer 50 also comprise one or more (for example, 2,3,4,5 kind) can reduce and/or the metal cation component of the metal ion that sorption (for example, absorption and/or absorption) is dissolved catch component.In some embodiments, catch layer 50 and comprise and a kind ofly catch component " TC1 ", and in another embodiment, catch layer 50 and comprise that two kinds are caught component " TC1 " and " TC2 ".
TC1 can be metal (for example, bismuth, tin, zinc, indium, cadmium, a lead); Metal oxide (for example, titanium oxide (TiO), iron oxide (Fe for example 3O 4Or FeO)) niobium oxide (for example NbO or NbO, 2); Metal hydride (for example, titantium hydride (TiH 2), zircoium hydride (ZrH 2), misch metal alloy hydride); Or salt (for example, slaine is as artificial gold (ZnS), bismuth sulfide (Bi 2S 3), iron sulfide (FeS)).In some cases, TC1 can be an organic material, for example oxalates (for example, magnesium oxalate (MgC 2O 42H 2Or tartrate (for example, tartro-bismuthate (Bi O)) 2(C 4H 4O 66H 2O)).In some embodiments, TC1 is organic complexing agent (for example, BTA, a tolyl-triazole).In some embodiments, TC1 can be metallo organic material (for example a, zinc diethyl dithiocarbamate).
Catch component TC1 and can have the more negative reduction potential of reduction potential than the metal cation component in the target dissolved metal ions.As a result, when TC1 contacted with the metal ion of dissolving, TC1 can be reduced into metal with the metal cation component of metal ion of dissolving.By after the TC1 reduction, metal is insoluble, and can prevent to pass anode by one of several layers in the barrier film (for example, can catch the layer of catching of metal).In some embodiments, catching component TC1 can have than the reduction potential of metal cation component of the metal ion of the dissolving reduction potential of 10mV to about 2100mV of breaking a promise.In some embodiments, TC1 has than the reduction potential of metal cation component of the metal ion of (for example, under pH16) dissolving reduction potential of 500mV to about 1500mV (for example, about 600mV) of breaking a promise.For example, if the metal ion of dissolving is to come from for example silver (II) material (for example, the Ag (OH) of silver oxide (AgO) negative electrode 4 2-), be zinc and catch component TC1, then under pH16, zinc can demonstrate the Ag (OH) than dissolving 4 2-In the break a promise reduction potential of 1850mV of the reduction potential of metal cation component.
In some cases, TC1 has the reduction potential more positive than the reduction potential of hydrogen (for example measuring) in electrolyte, so that TC1 can not cause the aerogenesis of hydrogen.For example, bismuth has than the reduction potential of the hydrogen reduction potential of (about 400mV) just.Perhaps, TC1 can have the reduction potential (for example in electrolyte measure) slightly more negative than the reduction potential of hydrogen.For example, TC1 can have than the break a promise reduction potential of the about 150mV of 1mV-of the reduction potential of hydrogen.Tin has the reduction potential than the reduction potential slightly negative (about 100mV) of hydrogen.In other cases, TC1 can have the reduction potential (for example in electrolyte measure) obviously more negative than the reduction potential of hydrogen.For example, TC1 can have than the break a promise reduction potential of the about 600mV of 150mV-of the reduction potential of hydrogen.In these cases, TC1 preferably has high liberation of hydrogen overpotential (for example, at alkaline electrolyte, for example among the 6N KOH, at 1mA/cm 2The liberation of hydrogen current density under the overpotential of the about 750mV of about 500mV-that measures), so that TC1 causes liberation of hydrogen with sizable speed.For example, although zinc have than the reduction potential of hydrogen break a promise 500mV reduction potential (when the two all in that pH is about when measuring in alkaline electrolyte for 16 times), zinc has high liberation of hydrogen overpotential (at 1mA/cm 2Current density under about 720mV).Therefore, under its rest potential, H 2Actual speed of separating out from zinc surface may very low (for example, about 0.02 microlitre/hr/cm 2, under at 60 ℃ and 760torr, measured in the 35.3%KOH of the ZnO with 2% dissolving).
Preferably, the product between the metal ion of TC1 and dissolving insoluble relatively in electrolyte (for example, about 10 -5Mol/l-about 10 -3Mol/l).Product between the metal ion of TC1 and dissolving is slightly soluble under the electrolytical situation therein, and the preferred reaction product does not influence the active material of electrode nocuously.
Can TC1 be joined according to many diverse ways and catch in the layer 50.For example, can be by in gel-in-matrix, disperseing the powder-form of TC1, and gained gel or suspension are applied on one of the sheet material component (for example, non-woven layer or selective membrane) of barrier film, catch in the layer thereby TC1 joined.As another example, can prepare the dispersion of TC1 in gel-in-matrix, and casting or coating form one deck on release liner.Then can dry this layer, take off from release liner, and be adhered on one of the sheet material component of barrier film.As another example, can be directly on one of sheet material component of barrier film paint or the ink-like dispersion of preparation and coating, printing or spraying TC1.In some embodiments, above-mentioned gel coat and/or paint or ink-like dispersion also can be used as the adhesive that respectively is pressed together layer by layer in the barrier film.As another example, can catch on the layer or within form TC1.For example, if TC1 is metal, then can by for example catch on the layer or within chemistry or electrochemical reduction slaine, thereby catch on the layer or within form metal.In this case, can be before the assembling laminated diaphragm, catch on the layer or within form TC1.
In some embodiments of barrier film 16, catch layer 50 and comprise that further another catches component.For example, the reaction between the metal ion of TC1 and dissolving obtains solvable product (for example, Bi 2O 3, Bi (OH) 3Or Bi (OH) 4 -), then catch layer 50 and can comprise that second catches component TC2.Catching component TC2 can react (for example, sorption) with solvable product, obtains insoluble product.In some cases, the TC2 that is under its unreacted state is insoluble relatively in electrolyte.For example, the solubility of TC2 in electrolyte can be about 10 -7Mol/l (for example, about 0.01mg/l)-Yue 10 -4Mol/l (for example, about 10mg/l).In other cases, TC2 is slightly soluble in electrolyte (for example, about 10 -3Mol/l or about 100mg/l).Preferably, TC2 does not influence the active material of electrode nocuously.TC2 can be titanium dioxide (TiO for example 2) or zirconium dioxide (ZrO 2).As an example, titanium dioxide and zirconium dioxide the two can absorb the Bi (OH) of dissolving 3, be formed on product insoluble among the 9N KOH.
One or more catch component can have the structure of opening (for example, porous) relatively.For example, catching component can be perforated foil or film, woven webs, wire rod and/or filament form.In some cases, catching component can be that powder type maybe can be a dust.
The structure of catching layer can provide the passage of ion and/or solvent transmission.Catching component and can form nonconducting network in catching layer.Catching component can be discontinuous relatively latticed form, and described network comprises the metallic particles (so that metallic particles does not contact usually each other) that is for example centered on by the adhesive polymeric matrix.Polymeric matrix can be a gel, and described gel allows the infiltration of electrolyte ion and electrolyte solvent.
Catch layer therein and comprise in two kinds of different embodiments of catching component TC1 and TC2, catch that component can be mixed or can be independently of one another (for example, be positioned at the distinct area of catching layer).For example, catch catching in the layer of component at bismuth-containing metal and the two conduct of zirconium dioxide, but blending bismuth metal and zirconium dioxide.Perhaps, bismuth metal and zirconium dioxide can be suspended in the independently subgrade of catching in the layer.For example, bismuth metal and zirconium dioxide can be suspended in the adjacent subgrade of polymer gel, and wherein one deck subgrade comprises that mainly bismuth metal and another subgrade mainly comprise zirconium dioxide.In some embodiments, the bismuth master metal will be suspended in first polymer gel, and zirconium dioxide mainly is suspended in second kind of different polymer gel adjacent with first polymer gel.This gel can be selected based on itself and employed compatibility of catching component.
The thickness of catching layer can be about 1 micron-Yue 500 microns (for example, about 65 microns).In some embodiments, catch the layer thickness be about 30%-about 70% of whole membrane thicknesses.
The diffusion of the metal ion of dissolving from negative electrode controlled and/or limited to selective membrane 52, thereby prevent to catch layer is full of dissolving in the short time period a metal ion.Electrolyte can pass selective membrane 52 usually.Selective membrane can be for example glassine paper or grafted polyethylene.The thickness of selective membrane can be about 10 microns-Yue 40 microns (for example, about 20 microns).In some embodiments, the thickness of selective membrane is about 10%-about 15% of whole membrane thicknesses.
Non-woven layer 54 is tunica fibrosa or the fabrics with good chemical and/or mechanical performance.For example, non-woven layer can have one or more following performances: homogeneous thickness (for example, 0.060mm ± 0.006mm); Uniform aperture; High tear strength; Chemical stability to cell electrolyte; The chemical stability of antianode and/or active material of cathode; High electrolyte absorption speed is (for example, greater than about 100g/m 2); High electrolyte osmosis and diffusion velocity; Low ion resistance rate; With low basic weight (for example, less than about 30g/m 2).Non-woven layer can provide the support for barrier film 16.Different with selective membrane 52, non-woven layer 54 does not have selectivity to the ion of dissolving usually.Non-woven layer is conductive electrolyte well, therefore can maintain electrolytical deposit between negative electrode and the anode.Non-woven layer 54 can be fibrous polymer fabric (for example, vinal and/or the rayon fiber that bonds together with polyvinyl alcohol adhesive).The thickness of non-woven layer can be about 30 microns-Yue 120 microns (for example, about 60 microns).In some embodiments, the thickness of non-woven layer is about 25%-about 60% of whole membrane thicknesses.Can be according to many diverse ways assembling barrier films 16.In some embodiments, at first assemble the layer of catching in the barrier film.In some embodiments, catch component (for example TC1 and TC2) and polymer binder solution, catch layer 50 thereby form by one or more of blended powder form.The example of polymer binder solution be contain the polyacrylic acid gelling agent solution (for example, 5% Carbopol 934), 25% the ethanol that gathers (acrylic acid) aqueous solution (for example, 20% Glascol E11) and 75% (or the aqueous solution of poly-(vinyl alcohol)) available from CibaSpecialty Chemicals available from Noveon Inc..After component and polymer binder solution are caught in blend, can go up this mixture of coating in release liner (for example, the Mylar of silicone coating).In some embodiments, can the thermoplastic polymer film of powder perhaps be arranged by the blowing load, form and catch layer 50 for example by extruding.In some cases, catch the suspension of component in viscose glue by preparing one or more, extrude this suspension then in sour curdling is bathed, the cellulose of formation regeneration/catch component composite material is caught layer 50 thereby form.
After layer is caught in formation, it can be incorporated in the barrier film 16.Can be incorporated in the barrier film thereby will catch layer by catching layer other layer lamination in barrier film.In some cases, (for example use scraper) and will catch layer directly to be coated on non-woven layer and/or the selective membrane.In some embodiments, catch the layer with non-woven layer isolated.Catching layer can control each assembly in the barrier film together.In some cases, at one or more layers other layer of barrier film, for example layer is caught in spraying and/or printing on the non-woven layer.
Preferably, prevent that the metal ion that dissolves from obtaining path around barrier film 16.In some embodiments, can (for example to use hotmelt) glued together for the seam of barrier film 16.In some cases, the bottom useful binders joint filler of barrier film pipeline or cavity (being that anode 14 is placed the volume of being determined by barrier film within it) is airtight.The bottom of barrier film pipeline or cavity can be pressed from both sides or be folded and be sealed.In some embodiments, independently end cup can form and be inserted in the barrier film pipeline, and perhaps the barrier film pipeline can be inserted in the end cup.End cup can comprise with the barrier film identical materials and/or can have the structure identical with barrier film.End cup can comprise any or combination in the barrier film component, perhaps can comprise one or more materials different with barrier film.It can be permeable or impermeable forming employed one or more materials of end cup.Seam between end cup and barrier film pipeline can be passed through adhesive seal.In some embodiments, the plastic resin stopper can be at the bottom of barrier film pipeline casting, so that carry out closure.In some cases, barrier film is made up of many (for example, 2,3,4) roll of material.
Negative electrode 12 comprises conductive auxiliary agent, adhesive and aforesaid active material (for example copper product).The example of active material of cathode comprises oxide (for example, cupric oxide (CuO), the cuprous oxide (Cu of copper 2O)); The hydroxide of copper (for example, Kocide SD (Cu (OH) 2), cuprous hydroxide (Cu (OH))); Cupric iodate (Cu (IO 3) 2); AgCuO 2LiCuO 2Cu (OH) (IO 3); Cu 2H (IO 6); The metal oxide of cupric or chalcogenide; The chloride of copper (for example, CuCl 2); Permanganate (for example, Cu (MnO with copper 4) 2).The oxide of copper can be stoichiometric (for example, CuO) or non-stoichiometry (for example, CuO x, 0.5≤x≤1.5 wherein).In some embodiments, negative electrode 12 comprises that about 65%-is about 99%, the preferably about 75%-about 95% and the copper product of about 95% weight of 85%-more preferably from about.After disperseing electrolyte, measure all wt percentage provided herein.Copper product in negative electrode 12 can comprise only cupric oxide, perhaps the mixture of copper product.For example, in the middle of the copper product in negative electrode 12, negative electrode can comprise that the permanganate of the chloride of copper of about 100% weight of about 5%-and/or copper and all the other are for example cupric oxide.
If negative electrode 12 comprises copper product, then negative electrode can discharge Cu (OH) 4 2-Or Cu (OH) 4 3-Ion is in electrolyte.The component of catching in the layer can form the copper metal with this ionic reaction.For example, when catching layer 50 when comprising bismuth, tin or zinc, then catching layer can be according to reaction shown below and Cu (OH) 4 2-Ionic reaction:
(2)2Bi+3Cu(OH) 4 2-→3Cu+Bi 2O 3+3H 2O+6OH -
(3)Sn+2Cu(OH) 4 2-→2Cu+SnO 2+2H 2O+4OH -
(4)Zn+Cu(OH) 4 2-→Cu+ZnO+H 2O+2OH -
Contain Fe when catching layer 3O 4The time, then catch layer usually as followsly with Cu (OH) 4 2-Reaction:
(5)2Fe 3O 4+Cu(OH) 4 2-→Cu+3Fe 2O 3+H 2O+2OH -
The layer of catching that contains titantium hydride can be as followsly and Cu (OH) 4 2-Reaction:
(6)TiH 2+3Cu(OH) 4 2-→3Cu+TiO 2+4H 2O+6OH -
Artificial gold is usually according to reaction shown below and Cu (OH) 4 2-Reaction:
(7)2SnS+2Cu(OH) 4 2-→2Cu+SnS 2+SnO 2+2H 2O+4OH -
Contain organic reducing agent, for example oxalates or tartrate catch the layer can with Cu (OH) 4 2-Ionic reaction forms the copper metal, and aldehyde, ketone, organic acid, carbon dioxide, carbonate and/or water.
Although described copper product, active material of cathode is copper product not necessarily.In some cases, the active material of negative electrode 12 can be silver compound (for example, Ag for example 2O, AgO), permanganate (for example, KMnO 4, Ba (MnO 4) 2, AgMnO 4), ferrate (for example, K 2FeO 4, BaFeO 4), nickel oxide, hydroxy nickel oxide, hydroxy cobalt oxide, manganese oxide, bismuth oxide or cobalt oxide.In general, active material of cathode can be to demonstrate partial solubility (for example, about 10 at least in it belongs to wherein the system of a part -7The about 1mol/l of mol/l-, about 10 -6Mol/l) any material.On September 16th, 2003 submit to and title for disclosing the example of active material of cathode among the temporary patent application No.____ of " Primary AlkalineBattery Containing Bismuth Metal Oxide " [lawyer's file number No.08935-295P01], at this by with reference to being introduced into.
Conductive auxiliary agent can increase the conductance of negative electrode 12.The example of conductive auxiliary agent is a graphite granule.Graphite granule can be any graphite granule that uses in negative electrode.This particle can be synthetic or nonsynthetic particle and they can be to expand or unexpansive graphite.In some embodiments, graphite granule is non-synthetic, unexpansive graphite granule.In these embodiments, the particle mean size of graphite granule can be less than about 20 microns, for example, about 2 microns-Yue 12 microns, perhaps about 5 microns-Yue 9 microns, as using Sympatec HELIOS analyzer measured.Non-synthetic, unexpansive graphite granule can be for example available from Brazilian Nacionalde Grafite (Itapecirica, MG Brazil (MP-0702X)).Perhaps or in addition, conductive auxiliary agent can comprise carbon fiber, as described in the U.S.S.N.09/658042 of the common transfer of submitting on September 7th, 2000 and the U.S.S.N.09/829709 that submits to April 10 calendar year 2001.In some embodiments, negative electrode 12 comprises one or more conductive auxiliary agents of about 10% weight of about 1%-.
The example of adhesive comprises polyethylene powders, polyacrylamide, portland cement and fluorocarbon resin, for example polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE).The example of polyethylene adhesive is sold (available from Hoechst) with trade name Coathylene HA-1681.Negative electrode 12 can comprise the adhesive of about 1% weight of for example about 0.1%-.
In some embodiments, can not use adhesive and/or not use assembling negative electrode 12 under the situation of carbon.In some embodiments, can utilize reactive sintering assembling negative electrode 12.As the example of reactive sintering, the blend of punching press 67%CuO and 33% copper powder in mould produces pellet.In air, calcine this negative electrode pellet down, thereby cause self-supporting conductive cathode pellet then at about 400 ℃-Yue 600 ℃.Utilize reactive sintering to make under the certain situation of negative electrode therein, a part of copper powder can be substituted by the copper fiber that meticulous weak point is cut, so that for example provide more by force and/or the negative electrode pellet of conduction more.
Anode 14 can be formed by employed any Zinc material in galvanic anode.For example, anode 14 can be a gel of zinc, and described gel of zinc comprises zinc metallic particles, gelling agent and trace mineral supplement, for example the aerogenesis inhibitor.In addition, a part of electrolyte is dispersed in the whole anode.
Zinc granule can be any zinc granule that uses in gel anode.The example of zinc granule is included in those described in U.S.S.N.08/905254, U.S.S.N.09/115867 and the U.S.S.N.09/156915, and these are transferred to the application's assignee and introduce by reference at this.Zinc granule can be a kirsite, for example contains hundreds of parts/1,000,000 parts indium and bismuth.Anode 14 can comprise the zinc granule of about 80% weight of for example about 67%-.
The example of gelling agent comprises polyacrylic acid, grafted starch material, polyacrylic salt, polyacrylate, carboxymethyl cellulose or its combination.This polyacrylic example is Carbopol940 and 934 (available from Noveon Inc.) and Polygel 4P (available from 3V), with the example of grafted starch material be that Waterlock A221 is (available from Grain Processing Corporation, Muscatine, IA).The example of polyacrylic salt is Alcosorb G1 (available from CibaSpecialties).Anode 14 can comprise the gelling agent of about 1% weight of for example about 0.1%-.
The aerogenesis inhibitor can be an inorganic material, for example bismuth, tin, lead and indium.Perhaps, the aerogenesis inhibitor can be an organic compound, for example phosphate, ionic surface active agent or non-ionic surface active agent.The example of ionic surface active agent is disclosed in U.S. Patent No. 4777100 for example, at this by with reference to being introduced into.
Anode 14 can comprise other material.For example, in some embodiments, anode 14 can comprise can reduce the metal of negative electrode of copper-bearing materials.Suitable metal comprises for example aluminium, magnesium, calcium, silicon, boron, titanium, zirconium, hafnium, lanthanum, manganese, iron, cobalt, chromium, tantalum or niobium.Can use the combination of binary, ternary, quaternary and other multi-component alloys of these metals, and those combinations that contain zinc and these metals.
Electrolyte can be any electrolyte that uses in battery.Electrolyte can be moisture or nonaqueous electrolyte.Aqueous electrolyte can be an alkaline solution, aqueous hydroxide solution for example, and for example the mixture of LiOH, NaOH, KOH or hydroxide solution is (for example, NaOH/KOH).For example, hydroxide aqueous solution can comprise the hydroxide materials of about 40% weight of about 33%-, for example about 9N KOH (KOH of about 37wt%).In some embodiments, electrolyte also can comprise the zinc oxide of about 4% weight at most, the zinc oxide of for example about 2% weight.
In some embodiments, electrolyte can be the aqueous solution (for example, the ZnCl of salt 2, NH 4Cl, ZnCl 2And NH 4The mixture of Cl, ZnSO 4, Zn (ClO 4) 2, MgBr 2, Mg (ClO 4) 2).
In some cases, electrolyte can comprise the salt (for example, trifluoromethanesulfonic acid lithium) that is dissolved in the nonaqueous solvents (for example, the mixture of dimethoxy-ethane, ethylene carbonate and propylene carbonate).
Electrolyte can comprise other additive.As an example, electrolyte can comprise the soluble material (for example, aluminum) of reduction (for example, suppressing) active material of cathode solubility in electrolyte.Among the U.S.S.N.10/382941 of the common transfer of submitting on March 6th, 2003 additive agent electrolyte has been described, its full content at this by with reference to introducing.
Shell 18 can be at battery, for example any shell of using always in the alkaline primary cell.In some embodiments, shell 18 comprises metal inner surface and outside non electrically conductive material, for example heat-shrinkable plastics.Randomly, conductive material layer can be arranged between inwall and the negative electrode 12.This layer can be along the inner surface of inwall, around the negative electrode 12 around or arrange along this both direction.This conductive layer can for example be formed by carbonaceous material.This material comprises LB1000 (Timcal), Eccocoat 257 (W.R.Grace ﹠amp; Co.), Electrodag 109 (Acheson Colloids Co.), Electrodag 112 (Acheson) and EB0005 (Acheson).For example disclosing the method that applies conductive layer among the Canadian Patent No.1263697, by reference it is being introduced in full at this.
Current-collector 20 is by suitable metal, for example brass manufacturing.Seal 22 can be for example by the nylon manufacturing.
Can use conventional method assembled battery 10.In some embodiments, can form negative electrode 12 by filling and the boring method of describing among the U.S.S.N.09/645632 that submits on August 24th, 2000.
In some cases, battery 10 can comprise hydrogen again in conjunction with (recombination) catalyst, to reduce the amounts of hydrogen in the battery, is wherein for example electroplated and zinc when oxidized when the copper metal, can generate described hydrogen.Suitable hydrogen combined catalyst is again disclosed in U.S. Patent No. 6500576 and No.3893870.Perhaps or in addition, can construct valve or exhaust outlet that battery 10 comprises pressure activation, for example described in U.S. Patent No. 5300371.
Battery 10 can be for example AA, AAA, AAAA, C or D battery.In other embodiments, battery 10 can be a non-cylindrical, for example, coin battery, button cell, prismatic battery or run-track shaped battery.Battery 10 can comprise a plurality of lobate electrodes, for example described in the U.S.S.N.09/358578 that submitted on September 21st, 1999.
Following embodiment is exemplary, and is not intended as restriction.
Embodiment 1
Preparation as described below has the battery diaphragm that bismuth is caught layer.
Adopt the high speed dispersion device, in poly-(acrylic acid)/ethanol/water solution, disperse bismuth meal (325 orders, promptly＜45 micron granularity).The load target of bismuth is the composition that obtains 20% volume bismuth meal and 80% volume polymer thing.
Adopt the knifing spreader of 25mil wet thickness, the mixture of coating thickness on the Mylar of silicone coating release liner.
Dry this material under environmental condition, and take off from release liner, 60 microns self-supporting film obtained.
Use the layer of catching of preparation as mentioned above to form laminated diaphragm.Catch the layer be positioned in the middle of the barrier film, and selective membrane at one end with non-woven layer at the other end.Assembling barrier film as described below.
With 54 microns poly-(vinyl alcohol) basic supatex fabric of water-wet.
Between 23 microns glassine paper sheet materials and poly-(vinyl alcohol) basic supatex fabric, accompany bismuth-poly-(acrylic acid) film (catching layer).Water in supatex fabric is enough to tackify bismuth meal-poly-(acrylic acid) film.Along film roll-in soft rubber roller, form the nexine contact then.
Dry this sandwich obtains having the fusible laminated diaphragm of good nexine under environmental condition.
The more alkaline barrier film of Zhi Bei laminated diaphragm and routine is caught the performance of copper.Materials used separates the moisture KOH electrolyte of cupric and the electrolyte of cupric not.
After 60 ℃ stored for 2 weeks down, when the alkaline barrier film by routine separated solution, by the UV-Vis spectrometry, the copper that is measured to 13ppm was present in the electrolyte of initial not cupric.Yet, adopt under the laminated diaphragm situation of bismuth-containing, detect the only copper of 4ppm.
Embodiment 2
Preparation as described below has the battery diaphragm that tin is caught layer.
Adopt the high speed dispersion device, in poly-(acrylic acid)/ethanol/water solution, disperse glass putty (325 orders, promptly＜45 micron granularity).The load target of tin is the composition that obtains 20% volume glass putty and 80% volume polymer thing.
Adopt the knifing spreader of 25mil wet thickness, the mixture of coating thickness on the release liner of silicone coating.
Dry this material under environmental condition, and take off from release liner, 60 microns self-supporting film obtained.
Use the layer of catching of preparation as mentioned above to form laminated diaphragm.Catch the layer be positioned in the middle of the barrier film, and selective membrane at one end with non-woven layer at the other end.Assembling barrier film as described below.
With 54 microns poly-(vinyl alcohol) basic supatex fabric of water-wet.
Between 23 microns glassine paper sheet materials and poly-(vinyl alcohol) basic supatex fabric, accompany tin-poly-(acrylic acid) film (catching layer).Water in supatex fabric is enough to tackify glass putty-poly-(acrylic acid) film.Along film roll-in soft rubber roller, form the nexine contact then.
Dry this sandwich obtains having the fusible laminated diaphragm of good nexine under environmental condition.
Embodiment 3
Preparation as described below contains the battery of laminated diaphragm.
The preparation of barrier film
Preparation has the battery diaphragm of catching layer according to following operation, and the described layer of catching comprises the subgrade of bismuth-containing and contain the subgrade of zirconia (zirconium dioxide) that this is two-layer.
At first, the desciccator diaphragm of preparation bismuth-containing.The high shear laboratory blender (available from Silverson L4RT-A) of use under 5000rpm slowly joins 25g Carbopol 934 in the 375g ethanol.Next, under mixing continuously, slowly add 100g Glascol E11 in this mixture, up to obtaining uniform viscous solution.Then, slowly add 150g bismuth metal (325 orders, 99.5% metal basis) in mixture, and continue to mix, even up to mixture.Use the film coated device then, 6 " wide rectangular in, the suspension of this thickness of coating on the Mylar of silicone coating release liner.The result is that thickness is 90 microns dry film.
In the independently method of carrying out in the film of preparation drying, preparation contains zirconic non-woven material.Use the high shear laboratory blender, in the 500g deionized water, disperse 50g zirconia nano-powder end (available from Aldrich Chemical Company).Next, continuing slowly to add poly-(vinyl alcohol) [mean molecule quantity (Mw)=85000-146000,87-89% hydrolysis] solution of 38.46g 13wt% under the mixing in this dispersion.Then, the 20g isopropyl alcohol is joined in the final dispersion, and poly-(vinyl alcohol) basic nonwoven sheet of 54 microns is pasted on the release liner.Then by toppling over this dispersion to the non woven fibre sheet material, this dispersion of dipping in nonwoven sheet, by the straight flange plastic spacer is passed through on the nonwoven sheet surface, remove excess solution, dry at ambient temperature this nonwoven sheet 1 hour repeats this method then.Use the Metal-Piercing device, punching goes out the circle of 1.3cm diameter from the supatex fabric.At 60 ℃ of down dry these supatex fabric.Compare with untreated sample and to show that load is 2.2 * 10 -3G ZrO 2-poly-(vinyl alcohol)/cm 2Supatex fabric.
Prepare diaphragm material according to following operation then.From release liner, take out bismuth metal-poly-(acrylic acid) thin-film sheet of 6 " * 8 ".This sheet material of spray solution with 75wt% ethanol-25wt% deionized water makes this film tackify.On the top surface of 6 " * 8 " sheet material of 23 microns cellophane film, place this film then.Afterwards, placement contains ZrO on the Free Surface of bismuth metal-poly-(acrylic acid) material 26 " * 8 " sheet material of the supatex fabric of-poly-(vinyl alcohol).Use the soft rubber roller, compress these layers and make it contact.Under environmental condition, carry out the barrier film that drying obtains having good interlaminar adhesion subsequently.
Form the barrier film cup according to following operation then.Cut the rectangular (4.6cm * 6.6cm), and change into the barrier film cup of sealing of above-mentioned diaphragm material.In PTFE piece material, get out the hole of 9.9mm diameter.Place the hotmelt (the 3748TC model is available from 3M) of about 0.15g fusion in the bottom of PTFE cavity.Barrier film is rectangular around the metal bar parcel, and described metal bar is coated with the dry film (available from Sprayon Products) of PTFE release coating.Bottom at metal bar inwardly folding (approximately 1mm) barrier film is immersed in the hotmelt of fusion then.Make this adhesive cools, and from the PTFE mould, take out barrier film.Remove the barrier film cup that metal bar obtains the double wrapped of bottom sealing subsequently.
Next, form battery according to following operation.Preparation has the negative electrode blend of following composition in small-sized blender: the 9N KOH of the expanded graphite of the cupric oxide of 89.3wt% (II), 4.5wt%, the Coathylene of 0.2wt% and 6wt%.In the AA of routine container, fill the cathode mix of 22.9g blend then.Add a part of cathode mix according to the order of sequence in this container and the middle powder that is squeezed in this container.After last extruding, use the drill of 9.9mm, on the Center Length of negative electrode, form cavity.Be inserted in the cathode cavity by barrier film cup then, and add the zinc anode slurry of about 1.2g 9N KOH electrolyte and about 5.6g routine, thereby make the AA battery sealing.The black box that contains the current-collector of tin-plated brass is placed in the open end of battery, and current-collector is immersed in the zinc slurry.Crimping seals this battery.
Form 3 AA batteries according to above-mentioned operation.After making, the open circuit voltage of battery (OCV) is about 1.4V.Store these 3 batteries down at 60 ℃ then.OCV drops to 1.1-1.0V fast, and then when down storing＞28 days for 60 ℃, battery keeps＞OCV of 1.0V.The similar battery made from the glassine paper-non-woven barrier film of routine (Duralam DT225, available from Duracell, Aarschot, Belgium) lost efficacy in 48-72 hour.
Barrier film can have the different number of plies (for example, 2 layers, 3 layers, 4 layers, 5 layers, 6 layers).In some cases, barrier film can have multilayer and catches layer.Can arrange the component of barrier film according to different modes.For example, and with reference to figure 3, barrier film 60 has and is contained in the mid portion 56 of catching layer 50 that is bonded on the side on the non-woven layer 54.On its opposite side, catch layer 50 and be connected on the selective membrane 52.Catch on layer 50 the side not being bonded to, non-woven layer 54 be bonded to second selective membrane 52 ' on.As shown in, selective membrane 52 and negative electrode 12 adjacent layouts, and second selective membrane 52 ' with anode 14 adjacent layouts.
The same with selective membrane 52, the diffusion of the metal ion of second selective membrane 52 ' may command dissolving.It also can slow down and/or limit the diffusion by the product of catching layer generation.The conductive electrolyte of second selective membrane 52 ' well, and for example can be glassine paper or grafted polyethylene.In some cases, second selective membrane 52 ' identical, and in other cases, second selective membrane 52 ' be different from selective membrane 52 with selective membrane 52.For example, different material and/or the thickness of second selective membrane 52 ' can have and selective membrane 52.
In Fig. 4, barrier film 70 be included in selective membrane 52 and second selective membrane 52 ' between catch layer 50.Selective membrane 52 and negative electrode 12 adjacent layouts, and second selective membrane 52 ' with anode 14 adjacent layouts.By on any side, having selective membrane, the catching layer 50 and can prevent to transship the metal ion of dissolving of barrier film 70.
Refer now to Fig. 5, barrier film 80 is included on the both sides by catching the non-woven material 54 of layer 50 and 50 ' encirclement.Catch the layer 50 and 50 ' can be identical or different.Catch layer and 50 be connected on the selective membrane 52, and catch layer 50 ' be connected to selective membrane 52 ' on.Selective membrane 52 and negative electrode 12 adjacent layouts, and second selective membrane 52 ' with anode 14 adjacent layouts.
By comprise two-layer catch the layer 50 and 50 ', barrier film 80 can demonstrate the capture ability of raising.As an example, when catching layer 50 and 50 ' when similar or identical, by catching still can be hunted down layer 50 ' absorb of soluble metal ions that layer 50 escapes from negative electrode.Have two-layer barrier film of catching layer and can realize effective cascade effect aspect its capture ability.For example, can catch the metal ion that layer (50) absorbs the dissolving of main content by first, wherein first catch these ions that layer (50) possibly can't be caught fraction.Because second catches layer (50 ') in the face of metal ion of less dissolving, so it still can keep original relatively situation, so that it can be caught effectively by first ion of not catching a small amount of dissolving that layer (50) absorbs.
In some embodiments, catch the layer 50 and 50 ' differ from one another.For example, in some cases (for example, Fig. 5), catch the layer 50 negative electrode 12 and catch the layer 50 ' between.In this case, can design and catch layer 50 and catch from negative electrode 12 metal ion that discharges, catch layer 50 ' be captured in and catch the accessory substance ion that forms in the ion trap courses of reaction that take place in the layer 50 and can design.Perhaps or in addition, can design and catch layer 50 ' directly and catch by catching the metal ions of the dissolvings that layer 50 escapes.
As an example, catch the Cu (OH) of dissolving when design of diaphragm 80 4 2-During metal ion, catch layer and 50 can contain the bismuth metal dust, and catch layer 50 ' can contain for example ZrO 2Nano particle.In catching layer 50, following capture reaction takes place:
(8)2Bi+3Cu(OH) 4 2-→3Cu+Bi 2O 3+3H 2O+6OH -
The Bi that in above-mentioned reaction, generates 2O 3Can be partially soluble in the 9N KOH electrolyte.The Bi of dissolving 2O 3Move out and catch layer 50, the two moves to negative electrode and anode.In some cases, the Bi of dissolving 2O 3Can cause the aerogenesis that hydrogen takes place on zinc anode.Can use catch the layer 50 ', by the dissolving Bi 2O 3Catch them before arrival or anode or the negative electrode, thereby avoid this problem.As an example, catch the layer 50 ' can comprise ZrO 2, so that it and the Bi that dissolves 2O 3Reaction as follows takes place:
(9)Bi 2O 3+ZrO 2→Bi 2O 3·xZrO 2
Bi 2O 3And ZrO 2Product be Bi 2O 3XZrO 2, it is (forming unknown) Bi 2O 3+ ZrO 2Insoluble complex compound.
In some cases, catch layer 50 ' further and comprise that second catches component, described second catches component can catch and the metal ion of catching layer 50 designed identical dissolving of catching.As an example, catch the layer 50 ' can comprise bismuth metal and ZrO 2Mixture.According to aforesaid equation 9, the bismuth metal can be caught the Cu (OH) that passes the dissolving of catching layer 50 4 2-Ion, and ZrO 2Can catch Bi 2O 3
All lists of references of herein quoting as proof, for example patent application, communique and patent are introduced by reference in its entirety at this.

Claims (30)

1. alkaline battery, it comprises:
The negative electrode that contains active material of cathode;
Anode;
Alkaline electrolyte; With
The barrier film that contains the ground floor and the second layer adjacent with described ground floor, described barrier film places between anode and the negative electrode, wherein ground floor comprises first material, the metal cation component of the ion that described first material can reduction of dissolved, and the ion of described dissolving comes from negative electrode.
2. the battery of claim 1, wherein Rong Xie ion is a multi-atomic ion.
3. the battery of claim 1, wherein first material has the reduction potential more positive than the reduction potential of hydrogen.
4. the battery of claim 1, wherein first material comprises metal.
5. the battery of claim 4, wherein metal is bismuth, tin, zinc or indium.
6. the battery of claim 1, wherein ground floor further comprises and contains the matrix that is selected from poly-(acrylic acid), poly-(vinyl alcohol), poly-(oxirane), poly-(vinylpyrrolidone), poly-(acrylamide), poly-(vinyl butyral) and gathers the composition in (4-styrene sulfonic acid).
7. the battery of claim 1, wherein ground floor has 1 micron-500 microns thickness.
8. the battery of claim 1, wherein the thickness of ground floor is the 30%-70% of membrane thicknesses.
9. the battery of claim 1, wherein the second layer comprises non-woven material.
10. the battery of claim 1, wherein the second layer comprises second material, the metal cation component of the ion that described second material can reduction of dissolved.
11. the battery of claim 1, wherein ground floor contacts with the second layer.
12. the battery of claim 1, its septation further comprise the 3rd layer.
13. the battery of claim 12, wherein ground floor places between the second layer and the 3rd layer.
14. the battery of claim 12, wherein the second layer comprises glassine paper or grafted polyethylene.
15. the battery of claim 14, wherein the 3rd layer comprises glassine paper.
16. the battery of claim 12, wherein the second layer comprises that non-woven material and the 3rd layer comprise glassine paper or grafted polyethylene.
17. the battery of claim 16, wherein ground floor places between the second layer and the 3rd layer.
18. the battery of claim 1, wherein Rong Xie ion comprises Cu (OH) 4 2-Perhaps Cu (OH) 4 3-
19. the battery of claim 1, its septation further comprises glassine paper or grafted polyethylene.
20. the battery of claim 19, wherein the thickness of glassine paper or grafted polyethylene is the 10%-25% of membrane thicknesses.
21. the battery of claim 1, its septation further comprises non-woven material.
22. the battery of claim 21, wherein non-woven material comprises vinal.
23. the battery of claim 21, wherein the thickness of non-woven material is 30 microns-120 microns.
24. the battery of claim 21, wherein the thickness of non-woven material is the 25%-60% of membrane thicknesses.
25. the battery of claim 21, wherein the second layer and anode are adjacent.
26. the battery of claim 1, its septation further comprises the second layer that contains glassine paper or grafted polyethylene.
27. the battery of claim 26, wherein the second layer and anode are adjacent.
28. the battery of claim 1, wherein negative electrode comprises copper product.
29. the battery of claim 1, wherein negative electrode comprises cupric oxide or Kocide SD.
30. the battery of claim 29, wherein negative electrode comprises cupric oxide.
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US20050079424A1 (en) 2005-04-14
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US7914920B2 (en) 2011-03-29
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US8288034B2 (en) 2012-10-16
US20120034508A1 (en) 2012-02-09

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